Two types of dimeric complexes [L
n2(hfa)
6(
![](/im<font color=)
ages/e
ntities/mgr.gif">
2-O(CH
2)
2NHMe
2)
2] a
nd [L
n(thd)
2(
![](/im<font color=)
ages/e
ntities/mgr.gif">
2,
![](/im<font color=)
ages/gifchars/eta.gif" BORDER=0 >
2-O(CH
2)
2NMe
2)]
2 (L
n= Y
III, Eu
III, Gd
III, Tb
III, Tm
III, Lu
III; hfa
- = hexafluoroacetylaceto
nato, thd
- = dipivaloylmetha
nato) areobtai
ned by reacti
ng [L
n(hfa)
3(H
2O)
2] a
nd [L
n(thd)
3], respectively, with
N,
N-dimethylami
noetha
nol i
n tolue
nea
nd are fully characterized. X-ray si
ngle crystal a
nalysis performed for the Tb
III compou
nds co
nfirms theirdimeric structure. The coordi
natio
n mode of
N,
N-dimethylami
noetha
nol depe
nds o
n the
nature of the
![](/im<font color=)
ages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-diketo
nate. I
n [Tb
2(hfa)
6(
![](/im<font color=)
ages/e
ntities/mgr.gif">
2-O(CH
2)
2NHMe
2)
2], eight-coordi
nate Tb
III io
ns adopt distorted square a
ntiprismaticcoordi
natio
n e
nviro
nme
nts a
nd are O-bridged by two zwitterio
nic
N,
N-dimethylami
noetha
nol liga
nds with aTb1···Tb2 separatio
n of 3.684(1) &Ari
ng;. I
n [Tb(thd)
2(
![](/im<font color=)
ages/e
ntities/mgr.gif">
2,
![](/im<font color=)
ages/gifchars/eta.gif" BORDER=0 >
2-O(CH
2)
2NMe
2)]
2, the
N,
N-dimethylami
noetha
nol actsas chelati
ng-bridgi
ng O,N-do
nor a
nio
n a
nd the Tb
III io
ns are seve
n-coordi
nate; the Tb1···Tb1A separatio
namou
nts to 3.735(2) &Ari
ng; withi
n ce
ntrosymmetric dimers. The dimeric complexes are thermally stable up to180
![](/im<font color=)
ages/e
ntities/deg.gif">C, as show
n by thermogravimetric a
nalysis, a
nd their volatility is sufficie
nt for qua
ntitative sublimatio
n u
nder reduced pressure. The Eu
III a
nd Tb
III dimers display metal-ce
ntered lumi
nesce
nce, particularly[Eu
2(hfa)
6(O(CH
2)
2NHMe
2)
2] (qua
ntum yield
![](/isubscribe/jour<font color=)
nals/jpcafh/112/i16/eq
n/jp711305ue10001.gif"> = 58%) a
nd [Tb(thd)
2(O(CH
2)
2NMe
2)]
2 (32%). Co
nsideratio
n of e
nergy migratio
n paths withi
n the dimers, based o
n the study of both pure a
nd Eu
III- or Tb
III-doped(0.01-0.1 mol %) Lu
III a
nalogues, leads to the co
nclusio
n that both the
![](/im<font color=)
ages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-diketo
ne a
nd
N,
N-dimethylami
noetha
nol liga
nds co
ntribute sig
nifica
ntly to the se
nsitizatio
n process of the Eu
III lumi
nesce
nce. The a
ncillaryliga
nd i
ncreases co
nsiderably the lumi
nesce
nce of [Eu
2(hfa)
6(O(CH
2)
2NHMe
2)
2], compared to [L
n(hfa)
3(H
2O)
2],through the formatio
n of i
ntra-liga
nd states while it is detrime
ntal to Tb
III lumi
nesce
nce i
n both
![](/im<font color=)
ages/gifchars/beta2.gif" BORDER=0 ALIGN="middle">-diketo
nates.Thi
n films of the most lumi
nesce
nt compou
nd [Eu
2(hfa)
6(O(CH
2)
2NHMe
2)
2] obtai
ned by vacuum sublimatio
ndisplay photophysical properties a
nalogous to those of the solid-state sample, thus ope
ni
ng perspectives forapplicatio
ns i
n electrolumi
nesce
nt devices.